DE2712542A1 - PHOSPACENE POLYMERS - Google Patents

Description

The invention relates to phosphazene polymers with at least partially regular structure.

Some phosphazene copolymers are already known, but they are all contain randomly repeating units and are characterized by the following statistically arranged structures can be:

P = N

hP = N- I
B.

-P = N- I B

in which A and B represent different residues. Some of these copolymers are described in U.S. Patents 3,271,330, 3,370,020, 3 370 026, 3 443 913, 3 515 688, 3 700 629, 3 702 833, 3 732 175, 3,844,983, 3,856,712, 3,856,713, 3,869,058, 3,883,451, 3,888,799, and 3,888,800.

^{Unsuccessful attempts have already been made to} polymerize the cyclic compounds N, P, (0CgHc) £ and ^N T ^P 3 ( ^c 5 ^H 5) ß (Allcock, "Phosphorous-Nitrogen Compounds", Academic Press, 1972, p. 323 -328). The polymerization of ^ ■ *? ■ *? 5C ^ H ₁ - ^succeeded (Allcock et al, Macromolecules, Vol 8, p 337 (1975).).

The polymers (I) according to the invention differ significantly from the polymer [NPCl ₂ ] _n (Allcock et al, US Pat. No. 3,370,020).

7 0 ^C JH Ί '-) / 1 0 η 7

that for every three repeating units there is a unit {■ NPC1 (OR *) 3 instead of a unit-f-NPC ^}. The polymer (II) likewise contains regularly present f NP (OR ¹ ) (OR ² )} units, in contrast to the completely statistical distribution in the known copolymers.

According to the invention it has now been found that cyclic polyphosphazenes of the formula

Cl Cl

T ^fra

clJ

in the row a group

represents, wherein the substituents R ,, if they are present, in Meta- or para position of the phenoxy nucleus are bound, χ a A number from 0 to 3, preferably 0 to 1 (and R, is preferably bonded in the para position, if χ is 1) and each of the radicals R is a linear or branched lower one Alkyl group, preferably having 1 to 10 carbon atoms, such as a Methyl, ethyl, η-butyl, sec-butyl or tert-butyl, 2-ethylhexyl or n-nonyl, a lower linear or branched one Alkoxy group, especially with 1 to 4 carbon atoms, such as a methoxy, ethoxy or butoxy group, a halogen atom, in particular a chlorine, bromine or fluorine atom, a cyano group or a nitro group or a substituted alkyl group or alkoxy group which is substituted, for example, with nitro, cyano or lower alkoxy groups or halogen atoms,

709839/1 OH?

can be polymerized to form polymers that have recurring units of the formula below.

in which η is more than about 2 to about 600 or more and R has the definition given above.

The polymers of the formula (I) can be reacted further, with Homopolymers or copolymers with recurring units of the formula below are formed,

in which η and R have the definition given above and

2 1

R stands for the same group as R or one of them is different denotes a group and represents a lower linear or branched alkyl group, preferably having 1 to 10 carbon atoms lower alkaryl group, substituted lower alkyl group such as one having lower alkoxy groups, halogen atoms, cyano groups or Nitro-substituted alkyl group or a group

< ⁴ _Z

^{in which the} radicals R, if present, are bonded in any sterically possible position of the phenoxy nucleus, preferably in the meta or para position, ζ denotes a number from 0 to 3, preferably 0 to 1 (and, if ζ denotes 1, R is preferably bonded in the para position) and in which each of the radicals R ^ is a lower straight-chain or branched alkyl group, a lower straight-chain or branched alkoxy group _r a halogen atom (preferably a chlorine, bromine or

0 ⁽ i Π "ί ⁰ I / 1 Π Π 7

Fluorine atom), a nitro group, cyano group or substituted Alkyl or alkoxy group (for example with nitro, cyano groups, Halogen atoms or lower alkoxy groups may be substituted).

Examples of the group OR include methoxy, ethoxy, propoxy, n-butoxy, sec-butoxy, tert-butoxy, octyl, phenoxy, tolyloxy, xylyloxy, benzyl, phenethyloxy groups, Chlorine or bromine atoms, methoxyphenoxy, propoxyphenoxy, p-nitrophenoxy, OCH ₂ GF ,, -, OCH ₂ C ₃ F ₇ -, OCH ₂ C ₃ FgCF ₂ H-, 2,2,3,3-tetrafluoropropoxy -, 3, ^ - dichlorophenoxy, 4-bromophenoxy, 2-chloroethylphenoxy, 2-chloroethoxyphenoxy and the like.

It is preferred that all R groups are the same

2
and that all radicals R are the same radicals; According to one embodiment of the invention, however, the radicals R can be mixed and / or the radicals R can be mixed. These mixtures can represent mixtures of different substituents or mixtures of different positional isomers. When making special polymers, steric hindrance must be taken into account. For example, it is readily apparent to those skilled in the art that steric hindrance requires that relatively bulky groups not be present in the ortho division of the phenoxy ring, since, as will be explained below, the group R _{2 is formed} by reacting a substituted metal phenoxide with a chlorine atom on the Phosphorus atom is formed. It is of course desirable that groups which sterically impede such a substitution reaction are omitted. Apart from the condition explained above, the choice of the various radicals R is obvious to the person skilled in the art on the basis of these explanations.

The repeating units of polymer II can be represented by the following formulas:

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P = N

(VI)

and

OR ² ρ = N OR ²

(V)

2n

wherein the ratio of unit to unit IV V is 1: 2, since the repeating unit formed by ring opening of the Triphosphazens (III). For example, typical polymer blocks are one or more of the blocks given below

OR ¹

i
- ρ = K-

OR ²

= N-

OR '

= N-

OR '

-P = N-OR "*

OR ¹

I.
-P = 11-

OR ²

OR ²

-P = N-

¹ 2
OR ^Z

I -P

¹ OR

= N -

OR ²

-P = 11

I 2 OR ' ²

0R ^J

OR "

or

- 'η

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The polymers described above Π as well as corresponding Polymers which have the reactive centers designated below with W can form free radicals with the aid of Initiators, for example peroxides, are crosslinked and / or cured at moderate temperatures, for example 93 to 177 ° C, the initiators being used in customary amounts and customary methods and devices being used.

The copolymers according to the invention can contain small amounts of substituents W, which in statistical distribution have a

2
Replace part of the -OR groups so that, for example, units of the following formulas can be present

0R ^J

and -

OR '

I W

N -

in which W represents a group that leads to a chemical crosslinking reaction is capable, such as an olefinically unsaturated, preferably ethylenically unsaturated monovalent radical, the one Having group which is capable of a further reaction at relatively moderate temperatures, the ratio of W to

(R + R) is less than about 1: 5. Examples of groups W include -OCH = CH ₂ ; -OR ₅ CH = CH ₂ ; -0-C = CH ₂ ; -OR ₅ CF = CF ₂ and the like

Groups which have unsaturation, in which the radicals R ₅ and Rg represent aliphatic or aromatic radicals and Rg preferably represents the group —CH ₂ -. These groups are able, at moderate temperatures (for example 93 to 177 ⁰ C) in the presence of radical-forming initiators, customary sulfur-containing hardeners

mn?

processing or vulcanization additives known in the rubber art, or other reagents, often even in their absence of accelerators to have a further reaction. Usual methods and processing devices can be used for this purpose be applied.

Examples of suitable free radical initiators include benzoyl peroxide, bis (2,4-dichlorobenzoyl peroxide), di-tert-butyl peroxide, Dicumyl peroxide, 2,5-dimethyl- (2,5-di-tert-butylperoxy) -hexane, t-butyl perbenzoate, 2,5-dimethyl-2,5-di- (tert-butylperoxy) -heptine-3 and 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane. The general classes of peroxide suitable for crosslinking thus include diacyl peroxides, peroxyesters and dialkyl peroxides.

Examples of sulfur-containing curing systems or sulfur-type curing systems include vulcanizing agents such as sulfur, Sulfur monochloride, selenium, tellurium, thiuram disulfide, p-quinone dioxime, Polysulfides and alkyl phenol sulfides. The vulcanizing agents specified above can be used together with accelerators, such as aldehyde amines, thiocarbamates, thiuram sulfides, guanidines and thiazoles, and accelerator activators such as Zinc oxide or fatty acids such as stearic acid can be used.

It is also possible to use, as the W group in the above formulas, monovalent radicals represented by the formulas below

(1) or (2) are represented:

7 8
(1) -OSi (OR) ^ R and other similar radicals containing one or more

QQ

contain reactive groups linked to silicon, (2) -OR NR H and other radicals containing reactive -NH linkages. In

7 8 Q of these radicals are the groups R, R and R each aliphatic, aromatic groups and acyl radicals. Like the groups discussed above, these groups are subject to further reaction at moderate temperatures in the presence of compounds that cause crosslinking. This is often the case for hardening The presence of a catalyst is desirable. The introduction of groups, such as group W, into polyphosphazenes,

is described in U.S. Patents 3,888,799, 3,702,833 and 3,844,983. The procedures described there are suitable for the purposes of the invention.

The amount of the groups W present in the copolymers influences the processability, smoke generation, glass transition temperature and a number of other properties of the copolymers. This Ratio also affects the ability of the copolymer to be foamed and properties such as rigidity dsr formed foams.

The cyclic polyphosphazenes of the formula III can, for example be prepared according to the general reaction scheme described by Dell et al, "Phosphorous Nitrogen Compounds Part XIII Phenoxy and p-Bromophenoxy-Chlorocyclotriphosphazatrienes ", J. Chem. Soc. (1965) 4070-4073.

This procedure generally uses the sodium salt of the desired phenol (HOR, where R is as defined above hat) in a suitable solvent such as tetrahydrofuran or dioxane. This phenoxide then becomes slow to the trimer, hexachloro cyclotripnosphases in a suitable Solvent as indicated above was added. This reaction is carried out at a low temperature to avoid side reactions to suppress. The use of substantial amounts of the solvent also promotes the formation of a uniform Product. The product obtained is then isolated. According to a preferred method of isolation, the Reaction solvent is replaced by a water-immiscible solvent and the solution is successively diluted with Acid, dilute base and water washed to remove unreacted starting materials and by-products. The organic Layer is then subjected to vacuum distillation.

The preparation of cyclic phosphazenes of the formula III is illustrated by the examples below.

709 8 39 / 10-2

example 1

Sodium phenoxide was made by reacting 8.0 parts of sodium with 44.0 parts of phenol in 1,800 parts of tetrahydrofuran. 120.0 parts hexachlorocyclotriphosphazene was added together with 1000 parts of tetrahydrofuran in a reaction vessel and the mixture was cooled to -78 ⁰ C. To the stirred reaction vessel, the Natriumphenoxidlösung previously prepared was added dropwise while the temperature was maintained at -78 ⁰ C, was completed by the addition over a period of 3 hours. The reaction mixture was then allowed to warm to room temperature.

The reaction mixture was then worked up in the following manner: the solvent was evaporated and the oil obtained was dissolved in petroleum ether. The ether solution was washed with 5% aqueous hydrochloric acid and then 5% aqueous sodium bicarbonate, followed by several water washes. The petroleum ether was then evaporated and the oil obtained was subjected to vacuum distillation, to obtain Phenoxypentachlortriphosphazen (Kp. 74 ⁰ C at 0.07 mm Hg).

Elemental analysis:

Theoretical: C 17.78, H 1.24, N 10.37, P 22.93 Found: C 17.65, H 1.24, N 10.44, P 22.88

Example 2
N ₃ P ₃ Cl ₅ (OC ₆ H ₄ -PF)

Sodium p-fluorophenoxide was made by reacting 4 parts of sodium with 26.9 parts of p-fluorophenol in 900 parts of tetrahydrofuran.

60 parts of hexachlorocyclotriphosphazene were added together with 500 parts of tetrahydrofuran in a reaction vessel and the mixture was cooled to -78 ⁰ C. The previously prepared solution of sodium p-fluorophenoxide was added dropwise as in Example 1

70983Π / 1Π0?

added and implemented. The product obtained was worked up in the same way as in Example 1, p-fluorophenoxypentachlorocyclotriphosphazene being obtained (boiling point 107 ^° C. at 0.02 now Hg),

Elemental analysis:

Theoretical: C 17.02, H 0.95, N 9.93, P 21.94 Found: C 17.36, H 1.00, N 9.86, P 21.85

Example 3
N ₃ P ₃ Cl ₅ (OC ₆ H ₅ -P-Cl)

Using p-chlorophenoxide, p-chlorophenoxypentachlorocyclotriphosphazene was produced with the aid of the procedure described in Example 1 (boiling point 126 ^° C. at 0.25 mm Hg).

Elemental analysis:

Theoretical: C 16.39, H 0.90, N 9.56, P 21.13 Found: C 16.34, H 0.82, N 9.42, P 21.05

Example 4

Using Na-p-methylphenoxide, p-methylphenoxypentachlorocyclotriphosphazene was produced with the aid of the procedure described in Example 1 (boiling point 130 ^° C. at 0.05 mm Hg).

Elemental analysis:

Theoretically: C 20.05, H 1.68, N 10.02, P 22.16 Found: C 20.18, H 1.69, N 10.08, P 22.09

Example 5
N ₂ P ₃ Cl ₅ (OC ₆ H ₄ -P-OCH ₃ )

Using Natriura-p-p-methoxyphenoxide Methoxyphenoxypentachlorcyclotriphosphazen was prepared by the procedure described in Example 1 (bp. 121 ⁰ C at 0.025 mm Hg).

■■ - η ο; .; -ί / "Ι 11 Γ; ~ *

Elemental analysis:

Theoretical: C 19.31, H 1.62, N 9.65, P 21.34 Found: C 19.58, H 1.79, N 9.67, P 21.43

Other cyclic trimers (III) can be prepared in the same manner as in the examples described above.

The polymers (I) are produced by thermal polymerization of the cyclic triphosphazenes by heating to a temperature of about 200 ^° C. for a period of 72 hours to 300 ^° C. for a period of 30 minutes. ^{That is to say, the compounds are heated to a temperature in the range from about 200 °} C. to about 300 ^° C. for a period of about 30 minutes to 72 hours, higher temperatures requiring shorter contact times and lower temperatures requiring longer contact times. The compounds must be heated for a time such that only a small amount of the unreacted starting material remains and a predominant amount of a high polymer has been formed. Such a result is generally achieved by observing the conditions of temperature and contact time explained above.

It is preferred that the thermal polymerization in the presence of an inert gas such as nitrogen, neon, argon or under vacuum, for example of about 10 mm Hg, since the reaction is slow in the presence of air. The usage however, such a gas is not critical. The presence of moisture is also preferably avoided.

The polymerization process is carried out according to the method described for the polymerization of {NPC1 ,,} in US Pat. No. 3,370,020 is.

The polymers formed by the thermal polymerization process are in the form of a polymer mixture of different polymers with different chain lengths. That means that

7noRiq / 1 nn?

The product of the thermal polymerization is a mixture of polymers of the formula I

where η ranges from about 2 to about 600 or more. For example, the recovered polymerization medium small amounts of a polymer in which η means 2, and contain predominant amounts of a polymer in which η means 600 or more. The medium can also contain polymers consisting of 3 to 599 or more repeating units, contain. The entire mixture of polymers can represent the starting material for the production of the polymer (II).

The polymers (I) show excellent elastomeric properties but are unstable to the humidity of the atmosphere.

Below are some examples of the preparation of the polymers (I). These examples are only intended to illustrate the invention, but not to limit it.

Example 6

A portion of the trimer from Example 1 was freed of oxygen with the aid of inert gas and transferred to a suitable one below 10 mm Hg Thick-walled reaction vessel enclosed and heated to 250 ° C for 15 hours. The polymerization was at this point ended as a glass ball with a diameter of 1.27 cm due to the increased viscosity of the molten mass stopped moving when the jar was turned over. It was terminated by cooling the vessel to room temperature. The polymer obtained had a glass transition temperature Tg of -49.1 ° C.

Elemental analysis:

Found (%): C 17.62, H 1.20, N 10.28, P 23.12

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Example 7

play 2 8 hours at 25O ⁰ C thermally polymerized. That gebil

In the same way as in Example 6, the trimer of the

sh I had finished polymers have a Tg of -47.6 ⁰ C.

Example 8

In the same way as in Example 6, the trimer of Example 3 was thermally polymerized at 250 ° C. for 10 hours. The polymer obtained had a Tg of -39 _f 3 C.

Elemental analysis:

Found: C 16.29, H 0.82, N 9.49, P 21.05

Example 9

In the same manner as in Example 6, the Triraere of the example was thermally polymerized for 4 18 hours at 250 ⁰ C. The polymer obtained had a Tg of -44.2 ° C.

Example 10

P ₃ Cl ₅ (OC ₆ H ₄ -P-OCH ₃ )} _n

In the same way as in Example 6, the trimer of the

: h tene polymers had a Tg of -43.7 ⁰ C.

For example, thermally polymerized for 5 6 hours at 25O ° C. The get-

The polymers (II) are formed with the aid of a process in which the polymer mixture (I), which is obtained in the thermal polymerization stage, is mixed with a mixture of compounds of the formulas

M (OR) _v and if desired

M (W) _V
709839/1002

is treated, in which M means lithium, sodium, potassium, magnesium or calcium, ν corresponds to the valence of the metal M.

ρ
and -OR and W have the meanings given above.

The polymer mixture is treated with the mixture of metal compounds at a temperature and for a time which is in the range from about 25 ^° C. for 7 days to about 200 ^° C. for 3 hours.

As in the above-explained polymerization stage, the polymer mixture is also here with the alkali or alkaline earth metal compounds treated at a temperature in the range of about 25 ° C to about 200 ° C for about 3 hours to 7 days, wherein lower temperatures require longer reaction times and higher temperatures allow shorter reaction times. These Conditions are, of course, applied in such a way that the reaction proceeds as completely as possible, i.e. that the complete replacement of the chlorine atoms in the polymer mixture by the corresponding ester groups of the alkali or alkali used as starting materials Alkaline earth compounds is guaranteed.

The esterification step explained above is carried out in the presence of a solvent. The solvent used for the esterification stage must have a relatively high boiling point have (for example, about 115 ⁰ C or above) and a solvent should represent both the polymers, as well as for the alkali metal or alkaline earth metal compounds. Additionally, the solvent must be substantially anhydrous, that is, must not be more water in the solvent or metal compounds, but to a water content of about 1 wt -% leads in the reaction mixture.. Avoiding the presence of water in the system is necessary to prevent the reaction of the available chlorine atoms in the polymer with water. Examples of suitable solvents include diglyme, triglyme, tetraglyme, toluene and xylene. The amount of solvent used is not critical and any amount can be employed

sufficient to dissolve the chloride-containing polymer mixture. As well as the polymer mixture, as well as the alkali or alkaline earth metal compounds can be in the form of a solution in an inert organic solvents can be used. However, it is preferred that at least one of the starting materials is in the form of a Solution is used in a solvent, which is also a solvent for the polymer mixture.

The amount of alkali metal or alkaline earth metal compound (s) used should be at least stoichiometrically equivalent to the number of cJers be available chlorine atoms in the polymer mixture. It will, however prefers to use an excess of the metal compounds in order to achieve complete conversion of all available chlorine atoms to ensure. If a mixture of metal compounds is used, it is generally the ratio of the individual that determines Alkali metal or alkaline earth metal compounds in the combined mixture, the ratio of groups associated with the Polymer main chain are linked. However, it is readily apparent to those skilled in the art that the type, and in particular the steric configuration of the metal compounds used can influence the relative reactivities. The mixing ratio

nis of the mixed radicals R in the esterified product can accordingly if necessary, regulated by using a stoichiometric excess of the more slowly reacting metal compound will.

Examples of alkali or alkaline earth metal compounds useful in the process of the present invention include the following Links :

Sodium phenoxide

Potassium phenoxide

Sodium p-methoxyphenoxide

Sodium 0-methoxyphenoxide

Natriuxn-m-methoxyphenoxide

7OP ^ n / 1 nn?

Lithium p-methoxyphenoxide Lithium o-methoxyphenoxide Lithium m-methoxyphenoxide potassium p-methoxyphenoxide Potassium o-methoxyphenoxide Potassium m-methoxyphenoxide Magnesium p-methoxyphenoxide Magnesium o-methoxyphenoxide Magnesium m-methoxyphenoxide Calcium p-methoxyphenoxide Calcium o-methoxyphenoxide CaIc ium-m-methoxyphenoxi d sodium-p-ethoxyphenoxide sodium-o-ethoxyphenoxide Sodium m-ethoxyphenoxide Potassium p-ethoxyphenoxide Potassium-o-ethoxyphenoxide Potassium-m-ethoxyphenoxide Sodium p-n-butoxyphenoxide sodium m-n-butoxyphenoxi d Lithium-p-n-butoxyphenoxide Lithium-m-n-butoxyphenoxy d Potassium-p-n-butoxyphenoxi d Potassium-m-n-butoxyphenoxide Magnesium p-n-butoxyphenoxide Magnesium m-n-butoxyphenoxide Calcium p-n-butoxyphenoxide Calcium m-n-butoxyphenoxide

709839/1

Sodium p-n-propoxyphenoxide Sodium o-n-propoxyphenoxide sodium m-n-propoxyphenoxide Potassium-p-n-propoxyphenoxide Potassium-o-n-propoxyphenoxide Potassium m-n-propoxyphenoxide Sodium p-methylphenoxide sodium o-methylphenoxide Natriura-m-methylphenoxide Lithium-p-methylphenoxide lithium-o-methylphenoxide Lithium-m-methylphenoxide Sodium p-ethylphenoxide sodium o-ethylphenoxide Sodium m-ethylphenoxide potassium p-n-propylphenoxide Potassium-o-n-propylphenoxide Kalium-m-n-propylphenoxi d Magnesium p-n-propyl phenoxide Sodium p-isopropyl phenoxide Sodium o-isopropyl phenoxide Sodium m-isopropyl phenoxide calcium p-isopropyl phenoxide Calcium o-isopropyl phenoxide Calcium m-isopropylphenoxide sodium p-sec-butylphenoxide Sodium m-sec-butylphenoxide

709839/1

Lithium p-sec-butylphenoxide Lithium-m-sec-butylphenoxide lithium-p-tert-butylphenoxide Lithium-m-tert-butylphenoxide Potassium p-tert-butylphenoxide Potassium m-tert-butylphenoxide Sodium p-tert-butylphenoxide sodium m-tert-butylphenoxide Sodium propene oxide sodium p-nonylphenoxide Sodium m-nonylphenoxide sodium o-nonylphenoxide Sodium 2-methyl-2-propene oxide, potassium butene oxide

and similar connections.

This process leads to the formation of a polymer blend Formula (II).

The reaction mixture obtained by this reaction step or esterification step is then subjected to a treatment to remove the Salt, which is formed by reaction of the chlorine atoms from the starting polymer mixture with the metal of the alkali metal or Alkaline earth metal compounds has arisen. The salt can be removed by simple precipitation and filtering off or it can be removed by any other suitable method, such as by neutralizing the reaction mixture, for example with an acid such as hydrochloric acid, and then Wash out with water.

7 η q sn q / 1 π η

The next step in the process is a fractional precipitation of the polymeric material to form the high polymer from low polymer and to separate from unreacted trimerea. the fractional precipitation is carried out by adding the esterified polymer mixture, preferably drop by drop, to a material which is a nonsolvent for the high polymer but a solvent for the low polymer and unreacted Trimer represents. This means that any material which is a nonsolvent for the polymers in which η is more than 350 means, and is a solvent for the remaining lower polymers, suitable to make the desired polymers to cut fractionally. Examples of compounds that can be used for this purpose include hexane, diethyl ether, Carbon tetrachloride, chloroform, dioxane, methanol, water and the like. Fractional precipitation of the esterified Polymer mixture should generally be carried out at least 2 times and preferably at least 4 times in order to achieve one large proportion of the low polymer from the polymer mixture to remove. The precipitation can be carried out at any temperature, but it is preferred that it be carried out at room temperature to undertake. The novel mixture according to the invention of high molecular weight Copolymers can then be recovered by filtration, centrifugation, decanting and the like.

Some examples of the preparation of polymers (II) are described below.

Example 11

An anhydrous solution of the polymer formed in Example 6 in toluene, which contained 31.2 parts of the polymer, was added to an anhydrous diglyme-benzene solution of 53.9 parts of sodium phenoxide at a temperature of 95 ^° C. with constant stirring. After the addition, the benzene was distilled off from the reaction mixture, bie a temperature of 115 to 116 ° C was reached. The reaction mixture was then refluxed for 60 to 65 hours. At the end

709839/1002

During this period, the polymer obtained was precipitated by pouring the reaction mixture into an excess of methyl alcohol. The polymer was stirred in methyl alcohol for 24 hours. Thereafter, the polymer was added to a large amount of water and stirred for an additional 24 hours. The polymer was then separated and dried. The homopolymer obtained was a semi-crystalline solid with a glass transition temperature (Tg) of -4.76 ⁰ C. The polymer was soluble in benzene, tetrahydrofuran (THF) and dimethylformamide (DMF). Films cast from THF were tough and opaque. The films did not burn and were water-repellent.

Elemental analysis:

Theoretical: C 62.34, H 4.36, N 6.06, P 13.40 Found: C 62.10, H 4.36, N 5.97, P 13.69

Example 12
£ NP (OC ₆ H ₄ -p-Cl) ₂ } _n

The procedure of Example 11 was repeated, with the modification that 15.0 parts of the polymer according to Example 8 were reacted with 30.8 parts of sodium p-chlorophenoxide. The homopolymer obtained in a yield of 79 % was a semicrystalline solid with a Tg of -1.54 ° C. The polymer was soluble in benzene, tetrahydrofuran, dimethylformamide and chloroform. Films cast from THF were tough and opaque. The films did not burn and were water-repellent.

Elemental analysis:

Theoretical: C 48.18, H 2.70, N 4.68, P 10.36 Found: C 47.90, H 2.63, N 4.49, P 10.28

Example 13

ίN ₃ P ₃ (OC ₆ H ₅ ) (OC ₆ H ₄ -P-Cl) ₅ J _n

The procedure of Example 11 was repeated, with the modification that 16.5 parts of the polymer of Example 6 were reacted with 37.1 parts of sodium p-chlorophenoxide. That in one yield Copolymers formed by 56,96 was a solid contained in

709839 / 1Od?

Benzene, THF and DMF was soluble. Foils potted from THF were tough and opaque. The films did not burn and were water-repellent.

Elemental analysis:

Theoretical: C 64.48, H 5.28, N 5.50, P 12.17 Found: C 64.34, H 5.22, N 5.42, P 12.30

Example 14

4 N ₃ P ₃ (OC ₆ H ^) (OC ₆ H ₄ -P-CH ₃ ) ^ _n

The procedure of Example 11 was repeated with the modification that 14.1 parts of the polymer of Example 6 were reacted with 27.3 parts of sodium p-methylphenoxide. The polymer formed in 40% yield was a solid which was soluble in benzene, THF and DMF. Films cast from THF were tough and transparent. The films did not burn and were water-repellent.

Elemental analysis:

Theoretical: C 64.48, H 5.28, N 5.50, P 12.17 Found: C 64.35, H 5.22, N 5.42, P 12.30

Example 15

i N ₃ P ₃ (OC ₆ H ₄ -PF) (OC ₆ H ₄ -P-CH ₃ ) ₅ } _n

The procedure of Example 11 was repeated with the modification that 18.9 parts of the polymer according to Example 7 were reacted with 35.3 parts of sodium p-methylphenoxide. The polymer obtained in a yield of 70% was a solid having a Tg of ⁰ +0.08 C and was soluble in benzene, THF and DMF. Films cast from THF were tough and transparent, did not burn and were water-repellent.

Elemental analysis:

Theoretical: C 63.00, H 5.03, N 5.37, P 11.89 Found: C 62.91, H 5.18, N 5.26, P 12.01

709839/1002

Example 16

■ [N ₃ P ₃ (OCgH ₄ -P-Cl) (OC ₆ H ₄ -P-CH ₃

The procedure of Example 11 was repeated with the modification that 15.0 parts of the polymer from Example 8 were reacted with 26.6 parts of sodium p-methylphenoxide. The polymer formed in 72% yield was a solid with a Tg of -3.65 ° C and was soluble in benzene, THF and DMF. Films cast from THF were tough and transparent, did not burn and were water-repellent.

Elemental analysis:

Theoretical: C 61.93, H 4.56, N 5.28, P 11.69 Found: C 61.83, H 4.72, N 5.18, P 11.52

Example 17

The procedure of Example 11 was repeated with the modification that 20.6 parts of the polymer from Example 9 were reacted with 44.1 parts of sodium p-chlorophenoxide. The polymer obtained in a yield of 41 96 was a solid having a Tg of ⁰ ₁ +2.06 C and was soluble in Jüenzol, THF and DMF. Foils cast from THF did not burn and were water-repellent.

Element analysis:

Theoretical: C 50.51, H 3.09, N 4.78, P 10.56 Found: C 50.32, H 3.05, N 4.77, P 10.78

Example 18

A solution of 15.5 parts of the polymer [N ₃ P ₃ Cl ₅ (OCgH _5)] in anhydrous toluene was added 200 parts of sodium pmethoxyphenoxid for a period of 1.5 hours at 90 ⁰ C to a stirred solution of. The sodium p-methoxyphenoxide solution was obtained by reacting 28.3 parts of p-methoxyphenol with 5 ₅ 1 part

709 8 3 9/1002

Sodium in 300 parts of anhydrous bis (2-methoxyethyl) ether and 100 parts of dry benzene have been obtained. After the addition, benzene was distilled off until a temperature of 115 to 116 ^° C. was reached. The reaction mixture was then heated to 115 to 116 ° C. for 60 to 70 hours with constant stirring. The polymer was precipitated in a large excess of methanol and washed in methanol for 24 hours. It was removed from the methanol, washed exhaustively with distilled water and dried. A colorless, rigid elastomer was obtained as the product.

Example 19

A solution of 16.5 g (0.205 equivalent) of the polymer [N ^ P ₅ Cl ₅ (OC ₆ H ₅ )] in 300 ml of anhydrous toluene became a stirred solution of ^{at 90 ° C. over a period of 1.5 hours} Given sodium p-chlorophenoxide. This sodium p-chlorophenoxide solution was obtained by reacting 31.6 g (0.246 mol) of p-chlorophenol with 5.6 g (0.241 mol) of sodium in 300 ml of anhydrous bis (2-methoxyethyl) ether and 100 ml of dry Benzene has been obtained. After the addition, benzene was distilled off until a temperature of 115 to 116 ^° C. was reached. The reaction mixture was then heated to 115 to 116 ° C. for 60 to 70 hours with constant stirring. The polymer was precipitated in a large excess of methanol and washed in methanol for 24 hours. It was removed from the methanol, washed exhaustively with distilled water and dried. The product obtained was a colorless fibrous material.

Using the same procedure, other homopolymers and copolymers as those described above can be prepared.

As already explained, the new polymers (II) according to the invention are thermally very stable. The mixtures are in specific organic solvents such as tetrahydrofuran, benzene,

709839/1 002

Xylene, toluene, dimethylformamide and the like, soluble and can from the solutions of the copolymers with evaporation of the Solvent to be deformed into foils. The polymers are water-resistant at room temperature and are not subject to hydrolysis at high temperatures. The polymers can be used to produce moldings, such as films, fibers, coatings and the like Molding compounds, etc. can be used. They can be mixed with various common additives, such as antioxidants, Ultraviolet absorbers, lubricants, plasticizers, dyes, pigments, fillers, such as litharge, magnesium oxide, calcium carbonate, Carbon black, alumina trihydrate and hydrated silicas, other resins and the like.

The polymers can be used to make foams that exhibit excellent flame resistance and in some Cases have little or essentially no smoke when heated in an open flame will. The foams can be made from filled or unfilled preparations using conventional foaming methods and using chemical blowing agents, i.e. chemical compounds produced in the original Are stable at room temperature and decompose or react at elevated temperatures, a cellular foam being obtained. Suitable chemical blowing agents include the following compounds:

Blowing agent °

Azobisisobutyronitrile 105-120

Azodicarbonamide (1,1-azobis-

formamide) 100 - 200

Benzenesulfonyl hydrazide 95-100

Ν, Ν'-blnitroso-Ν, Ν'-dimethylterephthalamide

Dinitrosopentamethylenetetramine 130-150 ammonium carbonate 58

ρ, ρ'-oxybis (benzenesulfonylhydrazide) 100-200

Diazoaminobenzene 84

709839/1002

Urea biuret mixture 90 - 140

a ^ '- azo-isobutyronitrile 90-140

Azohexahydrobenzonitrile 90-140

Diisobutylene 103

4.4 ^l -diphenyl-disulfonyl azide 110-130

Suitable foamable preparations include a mixture of the following ingredients:

Phosphazene copolymer (for example [N ₃ P ₃ (OC ₆ H ₅ ) (OC ₆ H ₄ -p-OCH ₃ ) ₅ ] _n filler (e.g. aluminum oxide trihydrate)

Stabilizer (e.g. magnesium oxide)

Processing aids (e.g. zinc starate)

Plasticizer resin (e.g. coumarone-indene resin, Coumar P-IO)

Blowing agents (e.g. Ι, Ι'-azobisformamide)

Activator (e.g. oil-treated urea)

Peroxide curing agents (e.g. 2.5-dimethyl-2,5-di- (t-butylperoxy) -hexane Peroxide curing agents (e.g. benzoyl peroxide)

The preparation given above is only intended to serve as an example, but it is evident that some or all of the additives given can be omitted, can be replaced by other functionally equivalent materials or that the proportions can be varied, as is known in the field of foam production .

In a suitable process, the components of the foamable Mixture mixed together to form a homogeneous mass. For example, a homogeneous film or web can be formed on a two-roll mill, preferably with one roll at room temperature and the other at

709839/1 002

0 -
2.5 100 parts
100 parts per 100
Parts
-10 " Il 2.5 - 10 It
Il 0 -
10 - 50
50 Il 10 - 40 Il 2.5 - 10 It 2.5 - 10

slightly elevated temperature, for example 38 to 49 ⁰ C is located. The homogeneous moldable mass can then be heated in order to obtain a foamed structure. This can be done, for example, using a mixture of a curing agent with a relatively low initiation temperature, such as benzoyl peroxide, and a curing agent with a relatively high initiation temperature, such as 2,5-dimethyl-2,5-di-t-butylperoxy) -hexane and partial precure in one closed form for about 6 to 30 minutes at 93 to 121 ° C and subsequent free expansion for about 30 to 60 minutes at 149 to 177 ° C. According to another embodiment, the foaming can be carried out by heating the foamable mass for 30 to 60 minutes at 149 to 177 ° C. using a high-temperature or low-temperature curing agent either alone or in combination. An advantage of using the foaming method with partial pre-curing is that the increase in the molecular weight of the foamable polymer before the foaming stage enables better control of the pore size and pore uniformity in the foaming stage. The degree of pre-cure desired depends on the ultimate foam properties desired. The desired foaming temperature depends on the type of blowing agent and the crosslinking agents present. The duration of the heating depends on the size and shape of the liquid to be foamed. The foams formed generally have a light brownish to yellowish appearance and their properties vary from flexible to semi-rigid depending on the glass transition temperature of the copolymers present in the foamable preparation. This means that the foam formed is all the more flexible, the lower the glass transition temperature of the polymer. As already indicated, inert, reinforcing or other fillers, such as aluminum oxide trihydrate, hydrated silicas or calcium carbonate, can be added to the polymeric foams, and besides these additives there can also be other customary additives, without the invention being restricted to the use of these additives.

709839/1002

Example 20

Production of the foamed polymer-CN ₃ P ₃ (OC ₆ H ₅ ) (OC ₆ H ^ -P-OCH ₃

To 100 parts of the copolymer -fN ₃ P ₃ (OC ₆ H ₅ KOC ₆ H ^ -P-OCH ₃ ) ₅ J _n »which had been prepared according to Example 20, 100 parts of aluminum oxide trihydrate, 5 parts of magnesium oxide, 5 parts were added Zinc stearate, 3 parts of coumarone-indene resin (Coumar P-IO), 30 parts of 1,1 - azobisformamide (Celogen AZ), 23 parts of an oil-treated urea (BIK-OT), 5 parts of 2,5-dimethyl-2, 5-di- (tert-butylperoxy) hexane and 5 parts benzoyl peroxide (78 % active, moistened with water) were added. The above ingredients were ground to ensure that all materials were homogeneously mixed. This mixture was then freely foamed for 10 minutes at 163 to 177 ° C. The flexible foam obtained was light brown in color and had a uniform structure with small cells. There were no signs of de! Amination or lateral delamination to be seen. A piece of the foam was heated in the flame of a Bunsen burner. It developed only very small traces of smoke. The sample did not burn when removed from the flame of the Bunsen burner. This sample therefore does not support combustion and was classified as non-flammable.

As already explained above, the polymers according to the invention can be crosslinked at moderate temperatures with the aid of customary radical and / or sulfur curing methods if small amounts of unsaturated groups W are present in the main polymer chain. The ability of these polymers to cure at temperatures below 177 ⁰ C, makes them particularly well suited as single and potting compounds, sealants, coatings and the like. These polymers are also suitable for the production of crosslinked foams which have significantly higher tensile strengths than uncured foams. The polymers are often crosslinked in the presence of inert, reinforcing or other fillers, and the presence of these fillers and other common additives is within the scope of the invention.

709839/100?

The foamed materials according to the invention can be used as moldings exist, such as in the form of foils, sheets, plates or tubes, which can be used, for example, as construction or insulating materials suitable. Such molded bodies are shown in the accompanying drawings.

In these drawings, Fig. 1 is a removable pipe insulation consisting of the two parts 1 and 2. 2 shows a plate made of a material according to the invention which, as the cut-open part shows, is foamed and has pores 4 has.

The moldings produced from the compositions according to the invention can, however, also be unfoamed, i.e. free from pores.

709839/10 02

lee J * rse

ite

Claims (7)

MARIAHILFPLATZ 2 Λ 3, MÖNCHEN POST ADDRESS: POST BOX 95 O1 6O, D-8OOO MÖNCHEN ARMSTRONG CORK COMPANY KARL LUDWIQ SCHIFF DIPL. CHEM. DR. ALEXANDER V. FÜNER DIPL. INTO THE. PETER STREHL DIPL. CHEM. DR. URSULA SCHUBEL- HOPF DIPL. INQ. DIETER EBBINGHiUS TELEFON (Ο89) 48 SO TELEX 6-93 See AURO D TELEGRAMS AUROMARCPAT MUNICH 22 March 1977 DA-K1709 phosphazene polymers PATENT CLAIMS 1. Polyphosphazene, characterized by repeating units of the formula in which η denotes more than 2 and R denotes a remainder of the following Formula stands 709839/1002 ORIGINAL INSPECTED wherein χ is a number from 0 to 3 and optionally present substituents R are bonded in the meta or para position to the phenoxy ring and each of the radicals R is one for itself lower alkyl group, lower alkoxy group, halogen atom, cyano group, nitro group, substituted lower alkyl or means substituted lower alkoxy group. 2. Polyphosphaζen according to claim 1, characterized in that R is a phenyl radical. 3- polyphosphazene according to claim 1, characterized in that R is a lower alkyl group means and χ stands for the number 1. indicates that R is lower alkyl or lower alkoxy 4. Polyphosphazene according to claim 3, characterized in that R is bound in the para position of the phenoxy ring is. 5 · Process for the preparation of a polyphosphazene with recurring Units of the formula in which η means a number greater than 2, thereby g e k e η η draws that one is a triphosphazene of the formula 709839/1002 Remainder in row denotes in which χ denotes a number from 0 to 3 and ϊτ denotes one or more optionally present substituents which, if present, are bonded in the meta or para position of the phenoxy ring, each of the radicals R being a lower alkyl group, lower alkoxy group , denotes a halogen atom, a cyano, nitro, substituted lower alkyl or substituted lower alkoxy group,
polymerized. 6. The method according to claim 5, characterized in that that the triphosphazene is thermally polymerized in an inert atmosphere. 7. The method according to claim 6, characterized in that that one polymerizes a triphosphazene in which χ 0 or 1 and OR is a phenoxy group, lower alkylphenoxy group or mean lower alkoxyphenoxy group. 8. Phosphazene copolymer, characterized by repeating units of the formula i N ₃ P _{3 n} 709839/1 OH? in which η is more than 2 and R is a radical of the formula where χ is a number from 0 to 3 and R is optionally represents present substituents which, if they are present, are bonded in the meta or para position of the phenoxy ring and the radicals R, independently of one another, are lower alkyl, lower alkoxy groups, halogen atoms, cyano, nitro, substituted lower ones Mean alkyl or substituted lower alkoxy groups, 2 1 and wherein the R group is different from the R group. 9. Copolymer according to claim 8, characterized in that both radicals OR and denoted phenoxy groups. 1 2 net that both radicals OR and OR are phenoxy groups or substituted 10. Copolymer according to claim 9, characterized in that the substituted phenoxy group is an alkyl-substituted or alkoxy-substituted phenoxy group. 11. Copolymer according to claim 8, characterized 2 net that a part of the groups OR through a to enter a group W capable of chemical crosslinking reaction is replaced, the ratio of W: (R + R) being less than about 1: 5 709839/1002 wearing. 12. Copolymer according to claim 11, characterized net that W is an ethylenically unsaturated monovalent radical means. 13 · Process for the preparation of a crosslinkable phosphazene copolymer, characterized in that one Polymer having repeating units of the formula below with at least one stoichiometric equivalent of an alkali or alkaline earth metal compound of the formula M (OR ² ) ν converts, where M is a lithium, sodium, potassium, magnesium or calcium atom and ν is the valence of the metal M, η is greater than 2 and R is a remainder represents, wherein χ is a number from 0 to 3 and R ³ stands for substituents which, if they are present, in meta- or para 709839/1002 ment of the phenoxy ring are bonded, each of the radicals R ^ for is a lower alkyl, lower alkoxy group, a halogen atom, a cyano, nitro, substituted lower alkyl group or substituted means lower alkoxy group and R is different from R and represents a lower alkyl group, lower alkaryl group, substituted lower alkyl group or a radical of the formula 4, wherein ζ is a number from 0 to 3 and each of the radicals R independently for themselves a lower alkyl, lower alkoxy group, nitro group, cyano group, a halogen atom or a substituted one means lower alkyl or substituted lower alkoxy group. 14. The method according to claim 13, characterized in that that one converts a polymer in which both groups OR and OR represent phenoxy groups or substituted phenoxy groups. 15. The method according to claim 14, characterized in that an alkyl or substituted phenoxy group alkoxy-substituted phenoxy group is present. 16. Process for the preparation of a phosphazene homopolymer, characterized in that one has a polymer with recurring units of the formula 709839/1002 with at least one stoichiometric equivalent of an alkali or alkaline earth metal compound of the formula M (OR ¹ ) _V converts, wherein M is a lithium, sodium, potassium, magnesium or Calcium atom and ν the valence of the metal M and η a number of more than 2 and FT a radical of the formula mean in which χ is a number from 0 to 3 and R is Substituents which, if they are present, are bonded in the meta or para position of the phenoxy ring, each of the Radicals R for themselves a lower alkyl, lower alkoxy group, a halogen atom, a cyano, nitro, substituted lower alkyl or substituted lower alkoxy group. 17. The method according to claim 16, characterized in that part of the compounds M (OR) is replaced by compounds M (OW) _V , wherein W is a group capable of entering into a chemical crosslinking reaction, and that a ratio of W: R of less than about 1: 5 is observed. 18. Foamed cellular molded body, consisting of a polymer and optionally customary additives, characterized in that it consists of a foamed phosphazene polymer with repeating units of the formula 709839/1 location? _; (0R ¹ ) (0R ² ; ^ _n consists in which η is a number greater than 2 and R is a residue of formula mean, in which χ is a number from 0 to 3 and the substituents R, if they are present, are bonded in the meta or para position of the fhenoxy ring and each of the radicals R ⁵ is a lower alkyl, lower alkoxy group, a nitro , Denotes cyano group, halogen atom, substituted lower alkyl or substituted lower alkoxy group and R is different from R. and a lower alkyl, lower alkaryl, substituted lower alkyl group or a radical of the formula 4 and ζ is O or 3 and each of the radicals R is a lower alkyl, lower alkoxy, nitro, cyano group, a halogen atom, a substituted lower alkyl group or represents a substituted lower alkoxy group. 19. Foamed cellular molded body according to claim 18, characterized 1 2 marked that both groups OR and OR Denote phenoxy or substituted phenoxy groups. 20. Foamed cellular molding according to claim 18 or 19, characterized characterized in that the substituted phenoxy group is an alkyl-substituted or alkoxy-substituted phenoxy group represents. 21. Cellular foamed molded body according to claim 18, characterized in that characterized in that the foamed polyphosphazene contains groups W capable of a chemical crosslinking reaction, the ratio of the groups W: (R + R) being less than about 1: 5. 22. Shaped body according to one of claims 18 to 21, characterized by the shape of a film, plate or one Rohrs. 7 0 8 8 3 9/1 Π Π ?